New insights into the mechanism of molybdenum-catalyzed asymmetric alkylation

The major features of the catalytic cycle, including structures of key intermediates, have been determined for the molybdenum-catalyzed asymmetric alkylation. The crystal structure of the π-allyl intermediate exhibits 3-point binding of an anionic ligand. Based on NMR analysis, this species adopts i...

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Bibliographic Details
Published in:Pure and applied chemistry 2004-01, Vol.76 (3), p.625-633
Main Authors: Krska, S. W., Hughes, D. L., Reamer, R. A., Mathre, D. J., Palucki, M., Yasuda, Nobuyoshi, Sun, Y., Trost, B. M.
Format: Article
Language:English
Subjects:
Alkylation
Catalysis
Crystal structure
Molybdenum
NMR
Nuclear magnetic resonance
Stereochemistry
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Summary:The major features of the catalytic cycle, including structures of key intermediates, have been determined for the molybdenum-catalyzed asymmetric alkylation. The crystal structure of the π-allyl intermediate exhibits 3-point binding of an anionic ligand. Based on NMR analysis, this species adopts in solution a structure consistent with that observed in the solid state. For the allylic alkylation, the crystal structure predicts the opposite stereochemistry vs. that observed experimentally, which suggests that either the reaction proceeds via a minor isomer (Curtin-Hammett conditions) or with retention of configuration. In addition, CO transfer, promoted by Mo(CO) , has been found to play a key role in catalyst turnover.
ISSN:0033-4545
1365-3075
DOI:10.1351/pac200476030625